Liquid cleaning agent or detergent composition

ABSTRACT

A liquid cleansing agent or detergent compositions which separates into at least two aqueous phases contains at least one surfactant in a concentration or less than 10% and at least one electrolyte in the concentration of less than 15%. Optionally, the composition contains less than 10% of organic solvent and less than 6% of sodium hexametaphosphate.

BACKGROUND OF THE INVENTION

The present invention relates to a liquid cleansing or detergentcomposition.

Whether cleaning hard surfaces, in particular in the kitchen orbathroom, or washing soiled fabric, it is a problem to remove bothinorganic and organic dirt. Whilst standard surfactants are used toremove most organic dirt, they are less effective and often even totallyineffective in removing inorganic dirt.

In order to remove inorganic dirt, it is therefore necessary to usecompounds, usually in aqueous solution, which are suitable for removingor detaching this dirt. Depending on the type of dirt, these compoundsmay be acid, neutral or alkaline.

In order to dissolve limestone deposits, which are generallyattributable to hardness-forming elements in the water, it is preferableto use acid aqueous solutions. Other inorganic dirt, for examplecontaining clay and/or pigment, is more readily removed using aqueoussolutions which have a neutral or alkaline pH in aqueous solution.

In either case, however, it has been found that if surfactants are addedto aqueous solutions devised as a means of removing inorganic dirt—so asto render them capable of removing organic dirt as well—theireffectiveness on inorganic dirt is significantly reduced.

The underlying objective of the invention is to provide a liquidcleansing or detergent composition which also has an efficient cleansingeffect on inorganic dirt in spite of containing surfactants.

SUMMARY OF THE INVENTION

This objective is achieved by the invention due to a liquid cleansing ordetergent composition, which separates into at lest two aqueous phaseswhen not in use, containing at least one surfactant in a concentrationof less than 10% by weight, and containing at least one electrolyte in aconcentration of less than 15% by weight provided the compositioncontains, if any at all, less than 10% by weight of organic solvent andless than 6% by weight of sodium hexametaphosphate.

DETAILS DISCLOSURES

In a preferred embodiment of the invention, surfactant(s) is(are)present in a concentration of between 0.5 and 6% by weight. Bypreference, the electrolyte(s) is(are) present in a concentration of atleast 0.5% by weight.

An alternative of the invention is characterised in that the electrolytecomprises at least one acid and the surfactant is at least partially asurfactant which has a net positive charge given the pH value of thecomposition.

In a preferred embodiment of this alternative composition proposed bythe invention, the concentration of acid is 0.5 to 15% by weight.

In another preferred embodiment of this alternative composition proposedby the invention, the concentration of acid is between 7 and 10% byweight.

It is more especially preferred if the pH value of the composition isbelow 4.

The acid(s) preferably used in this alternative of the compositionproposed by the invention is(are) selected from the group consisting ofphosphoric acid, amidosulphonic acid and mixtures thereof.

The preferred surfactant(s) is(are) selected from the group consistingof the quaternary ammonium salts, amines, amine oxides, betaines,sulpho-betaines and mixtures thereof.

In a second alternative proposed by the invention, the compositionpreferably contains at least one builder or a builder system, at leastone alkaline or alkalising compound or mixtures thereof.

By preference, the builder(s) or builder system and the alkaline oralkalising compound(s) is(are) present in a concentration of from 0.5 to6% by weight.

By particular preference, the surfactant contains, at least in part, atleast one cationic surfactant.

In a preferred embodiment, the composition proposed by the inventioncontains at least one other compound which promotes phase separation.

In one alternative, this may be a compound which promotes phaseseparation by separating out the salts, for which purpose an alkalimetal, earth alkali metal or ammonium salt of an inorganic acid,preferably sodium chloride, may be considered in particular.

In another alternative, the compound to promote phase separation may beone which comprises at least a hydrophobic part and at least an anionicgroup. By preference, this will be an anionic surfactant, xylol or cumolsulphonic acid or salts or mixtures thereof.

In a preferred embodiment, the composition proposed by the invention ischaracterised in that it contains at least one perfume and/or acolouring agent.

The invention also relates to the use of a composition, which separatesinto at least two aqueous phases when not being used and contains atleast one surfactant, as a cleanser or detergent.

One of the aforementioned compositions proposed by the invention is usedfor this purpose.

One particularly preferred embodiment relates to the use of such acomposition containing at least one acid for removing limestone depositsand the compositions listed above are preferably also used for thispurpose.

Another embodiment of the composition proposed by the invention relatesto the use of at least one electrolyte in a liquid cleansing anddetergent composition containing at least one surfactant to promoteseparation of the composition into at least two aqueous phases in orderto improve the effectiveness of the composition as a cleansing agent ordetergent.

Finally, the invention also relates to the use of xylol or cumolsulphonic acid or salts thereof in a liquid cleansing and detergentcomposition containing at least one surfactant and at least one acid topromote separation of the composition into at least two aqueous phasesfor improving the removal of limestone deposits.

Surprisingly, it has been found that by formulating a cleansing agent ordetergent to produce a composition that separates into at least twoaqueous phases when not in use leads to an unexpected improvement in thecleansing effect of such compositions, and in particular the dual effectagainst both organic and inorganic dirt. If such a composition is shakenor mixed before or during use, a dispersion is produced enabling ahomogeneous application on the surface or substrate. Both on the surfaceor substrate and in the container, this dispersion separates relativelyquickly again in the static state to form separate aqueous phases.

Without wanting to claim such to be the theory, it is assumed that thisseparation on the surface to be cleaned or the substrate to be cleanedis at least one of the reasons behind the superior cleansing effect thathas been discovered, since the negative counter-effect of the compoundsused for the different cleaning purposes is at least reduced, inparticular the negative influence of the surfactant or surfactants onthe effectiveness of the aqueous solutions in cleaning inorganic dirt.

Cleansing or detergent compositions which separate into two or moreaqueous phases have not been known before. Such compositions have beenpreviously described in relation to cosmetics and body care products(e.g. shampoo).

For example, GB-A-1 247 189 discloses a liquid composition for use as ashampoo or similar, which contains a surfactant, a water-miscibleorganic solution and an electrolyte, the relative proportions of theelectrolyte and the organic solvent being such that the compositionseparates into two aqueous phases. When shaken, such compositions form atemporary oil-in-water emulsion and separate into two phases again whenleft to stand. The compositions need to contain a significant amount oforganic solvent and/or electrolyte.

Shampoo compositions which also separate into two aqueous phases whenleft to stand are known from EP 0 116 422 A1 and 0 175 485 A2. In thecase of EP 0 116 422 A1, however, the contents—in addition tosurfactant—must include at least 6% of sodium hex ametaphosphate. In thecase of EP 0 175 485 A2, the minimum amount of surfactant contained inthe composition is 11%. Furthermore, the phase separation, which is thedesired objective, is produced only if special complexing agents such asorganophosphonates, aminocarboxylic acids, etc., are used.

Surprisingly, it has been found that a liquid cleansing or detergentcomposition which separates into at least two aqueous phases when leftto stand can be obtained using a relatively low content of surfactantand electrolyte, without it being necessary to incorporate additionalsubstances to produce this effect.

Analyses conducted on the two phases of the composition proposed by theinvention which occur normally have shown that the top phase containsthe surfactant(s), the perfume(s) and optionally the colour agent(s),whilst the remaining ingredients, in particular the electrolyte, areessentially evenly distributed in both phases.

What appears particularly notable is the fact that the composition canbe readily adjusted so that the volume of both phases is more or lessidentical. If the volume of the two phases is unevenly distributed, itmay help to add a small quantity of a non-ionic surfactant in order toproduce the two phases in the same volumes as required.

In addition to producing the desired phase separation, a surprisinglylow content of surfactant and electrolyte and a superior cleansing ordetergent effect, it has surprisingly also been found to be of advantageif an optionally used perfume remains more or less exclusivelyconcentrated in the top phase, as mentioned above. This is an advantagebecause on the one hand the essential purpose of adding a perfume to acomposition of this type is to mask other undesirable odours andaccordingly, the desired “masking effect” can best be produced in thetop phase. On the other hand, in the preferred situation—i.e. when thetwo phases are of more or less equal volume—if the perfume isconcentrated in the top phase, it is possible to reduce the perfumecontent in the composition as a whole by about a half, which makes for asignificant saving in costs, particularly if more expensive perfumes areused.

With the acid compositions proposed by the present invention, apart fromthe quaternary ammonium salts, amines, amine oxides, betaines andsulpho-betaines mentioned above, all other surfactants which have a netpositive charge in a composition of this pH are clearly also suitable.

The acids specified as a means of removing limestone deposits, i.e.phosphoric acid and amidosulphonic acid, are also not the only possiblechoice. Other acids which might be used include, for example, citricacid, maleic acid, Bernstein's acid, glutaric acid, adipic acid,hydrochloric acid, etc.

Apart from the builders or builder systems or alkaline or alkalisingcompounds specifically mentioned above, other compounds or mixtureswhich exhibit the requisite cleansing effect on inorganic stains arealso suitable for the present invention. Optionally, cationicsurfactants such as those mentioned above may be used in the neutral oralkaline compositions proposed by the invention.

Clearly, the compounds used to promote phase separation are notrestricted to the salts or organic compounds specifically mentionedabove.

As stated earlier, the addition of a (usually small) quantity ofnon-ionic surfactant may be helpful in producing the two aqueous phasesin more or less equal volumes. Generally speaking, there are no specificrestrictions as to the non-ionic surfactants that may be used.Accordingly, all known non-ionic surfactants are suitable, in particularfatty alcohol ethoxylates and alkylphenol ethoxylates.

The selection and quantity of appropriate perfumes and colouring agentswill essentially depend on aesthetic factors and the stability of thesecompounds in the compositions proposed by the invention and present noparticular difficulty for the person skilled in this field.

Other advantages and features of the invention will become clear fromthe examples set out below:

EXAMPLES I TO V

Various compositions as proposed by the invention, with delayedre-soiling, containing an acid are set out in Table I below.

TABLE I % weight Components Example I Example II Example III Example IVExample V Amidosulphonic 5 5 5 5 5 acid Phosphoric acid 3.75 3.75 3.753.75 3.75 Alkyl(C₁₆)- 2.5 1.5 — — — trimethyl ammonium chlorideOleyl-bis-(2- — — 1.9 — — hydroxyethyl)- methylammonium chlorideOleyl-bis-(2- — — — 3 — hydroxyethyl)- amine Lauryldimethyl — — — — 1.8amine oxide Sodium cumol 1.42 0.8 0.65 0.8 0.63 sulphonate Sodiumchloride — — — 0.5 — Perfume 0.15 0.15 0.15 0.15 0.15 Colouring (Acid —0.0015 0.0015 0.0015 0.0015 Blue 80) Water — Rest Rest Rest Rest

Although it does not appear to be decisive in terms of the result, thefollowing sequence in which the components are added to water to producethe compositions proposed by the invention clearly seems to produce anadvantage:

1. Water

2. Electrolytes (acid(s), sodium chloride)

3. Surfactant(s), perfume(s), colouring agent(s).

4. Sodium cumol sulphonate.

In all cases, the composition distinctly separated into two aqueousphases of more or less equal volume when left to stand and analysis ofthe individual phases showed that the surfactant, colouring agent andperfume were contained almost exclusively in the top phase whilst theacids and the sodium cumol sulphonate acting as the hydrotrope were moreor less evenly distributed in both phases.

The limestone cleansing action of the compositions proposed by theinvention were investigated on a test model. As a comparative example, asingle-phase composition of essentially the same composition as thecompositions of examples I, II and IV respectively was used although thesodium cumol sulphonate was replaced with water.

In order to determine the lime-dissolving capacity of these compounds, amarble cube in a metal basket was completely immersed in thecorresponding solution for a period of 30 minutes and the weight loss ofthe marble cube as a % determined after 1, 2, 5, 10 and 30 minutes.

In each case, the 2-phase formulation homogenised by shaking beforehandwas tested in comparison with the single-phase comparative formula withan identical content of acid and surfactant. With the 2-phase formula,care was taken to ensure that a phase separation, which as a rulestarted after a few minutes, was prevented by moving the basket, whichwas placed at approximately half height, up and down.

The test method was selected because it provided a good simulation ofthe actual conditions under which the corresponding detergent would beused.

TABLE 2 Lime-dissolving capacity as a % over time: 1 min. 2 min. 5 min.10 min. 30 min. I 0.41 0.78 1.73 3.37 9.97 I′ 0.41 0.72 1.93 3.07 8.37(Comparative example) II 0.51 0.98 2.27 4.40 11.08 II′ 0.44 0.79 1.723.21 8.93 (Comparative example) IV 0.47 0.80 1.73 3.23 9.39 IV′ 0.220.41 0.93 1.80 5.56 (Comparative example)

The results set out above demonstrate that the shaken 2-phase formula isclearly superior in lime-dissolving capacity than the correspondingsingle-phase formula.

The same positive results were produced when sodium cumol sulphonate wasreplaced with corresponding quantities of sodium xylol sulphonate.

EXAMPLE VI

Another acid detergent composition proposed by the invention is set outin Table 3 below.

TABLE 3 % weight Components Example VI Alkylbenzol sulphonate 3Phosphoric acid 3.7 Amidosulphonic acid 5 Alkylethoxylate-C9, 1 11-12EOPerfume 0.15 Colouring agent 0.0015 (Acid Blue 80) Water Rest

Instead of a salt of cumol or xylol sulphonic acid, alkylbenzolsulphonate was used as an anionic surfactant in this composition. Thetests for lime-dissolving capacity described above in relation to thepreceding examples also showed superior performance compared with acorresponding single-phase formula, although the effect was not sosignificant as using sodium cumol sulphonate or sodium xylol sulphonate.

EXAMPLES VII TO XV

Various neutral or alkaline disinfectant compositions proposed by theinvention are set out in Table 4 below.

TABLE 4 % weight Components Example VII Example VIII Example IX ExampleX Sodium carbonate 0.75 0.75 — — Sodium chloride — — — — Sodium sulphate0.75 2 2 — Sodium tripolyphosphate — 1.5 — — Potassium tripolyphosphate— — — — Phosphonate — — — — EDTA — — — — HEDP — — — — Disilicate — — — 3Metasilicate — — 2 — Didecyldimethyl 2.8 2.8 2.8 2.8 ammonium chloride¹C₁₂₋₁₆-benzyldimethyl — — — — ammonium chloride² Non-ionic surfactant(FAO, 0.75 — 2 2 C9-11, 6-EO) Non-ionic surfactant (FAO, 4 — — — C9-11,2.5-EO Amphoteric surfactant — — 0.9 0.9 Esterquat 1 — — —Dimethyloleylamine 1.25 — — — Fatty alcohol C₇-C₉ — — — —Cocoamidopropyl betaine — 2.7 — — C₁₂-C₁₄ glucamide 50% — — — —Propylene glycolmethyl — — — — ether Perfume 0.2 0.2 0.2 0.2 Colouringagent (Acid Blue 0.0015 0.0015 0.0015 0.0015 80) Water Rest Rest RestRest % weight Example Example Example Example Example Components XI XIIXII XIV XV Sodium carbonate 0.5 0.75 0.75 0.75 0.75 Sodium chloride 0.8— — — — Sodium sulphate — 2 3 2 0.5 Sodium tripolyphosphate 4 1.5 — — —Potassium tripolyphosphate 4 — — — 3 Phosphonate 0.1 — — — — EDTA — — —0.8 — HEDP — — 1.2 — — Disilicate — — — — — Metasilicate — — — — —Didecyldimethylammonium — — 2.8 2.8 2.8 chloride² (C₁₂₋₁₆-benzyldimethyl0.4 — — — — ammonium chloride)² Non-ionic surfactant (FAO, — 0.5 2 20.75 C9-11, 6-EO) Non-ionic surfactant (FAO, — — — — C9-11, 2.5-EOAmphoteric surfactant 3 2.55 0.9 0.9 0.9 Esterquat — — 0.5 — —Dimethyloleylamine — — — — 1.5 Fatty alcohol C₇-C₉ — 2 2 2 —Cocoamidopropyl betaine — — — — — C₁₂-C₁₄ glucamide 50% 3 — — — —Propylene glycolmethyl ether 3 — — — — Perfume 0.2 0.2 0.2 0.2 Colouringagent 0.0015 0.0015 0.0015 0.0015 0.0015 (Acid Blue 80) Water Rest RestRest Rest Rest ¹ca. 70% solution in isopropanol ²ca. 50% solution inisopropanol

In all cases, there was a clear separation of the composition into twoaqueous phases of approximately equal volume when left to stand and ananalysis of the individual phases indicated that the surfactant,colouring agent and perfume were almost exclusively contained in onephase whilst the other components, in particular the builder or alkalinecompound, were more or less equally divided between the two phases.

The cleansing effect of the two compositions proposed by the inventionwere investigated on a test model. The test structure was as follows:

The following ingredients were mixed in the specified sequence andstirred for two hours:

15% clay, screened through 250 μm

10% Myritol7 318 (capryl-capringlyceride, Henkel)

10% corn starch

15% CaCO₃

10% FeCI₂

40% tap water.

Prior to use, the mixture was thoroughly stirred again in order toproduce a homogeneous solution. This standard dirt (referred to as“pigment/grease dirt”) was applied using an appropriate coating devicein a coating thickness of 100 μm on enamel strips (10×40 cm). The stripswere stored at room temperature for at least the days in order to obtaina uniform drying process.

The cleaning tests were conducted using an automatic wiping machine(Erichsen). 2 ml of the composition proposed by the invention wereapplied in each case on a damp sponge. The number of wiping cycles was20.

The cleaned strips were assessed visually. Taking the bottom phaseessentially containing no surfactant as a reference value, the topphase, which contained surfactant, exhibited a markedly superiorcleansing effect and a significantly superior cleansing effect for theshaken mixture.

Cleansing performance (10 = 100% clean; 1 = no cleansing effect)Examples XII XIII XIV XV Shaken mixture 8 9 9 8 Bottom phase 6 7 8 6 Topphase 3 2 6 3

The features of the invention disclosed in the description above and inthe claims may essentially be used individually or in any combination toimplement the invention in its various embodiments.

What is claimed is:
 1. Liquid detergent or cleansing composition whichseparates into two aqueous phases when left to stand, containing atleast one surfactant in a concentration of less than 10% by weight,containing at least one electrolyte in a concentration of less than 15%by weight, and containing at least one other compound which promotesphase separation and comprises at least one hydrophobic element and atleast one anionic group, provided the composition contains, if any atall, less than 10% by weight of organic solvent and less than 6% byweight of sodium hexametaphosphate.
 2. Composition according to claim 1,wherein the surfactant(s) is (are) present in a concentration of 0.5 to6% by weight.
 3. Composition according to claim 1, wherein theelectrolyte(s) is (are) present in a concentration of at least 0.5% byweight.
 4. Composition according to claim 1, wherein the electrolytecomprises at least one acid and the surfactant contains at leastpartially at least one surfactant which has a net positive charge giventhe pH value of the composition.
 5. Composition according to claim 4,wherein the concentration of acid is 0.5 to 15% by weight. 6.Composition according to claim 5, wherein the concentration of acid is 7to 10% by weight.
 7. Composition according to claim 4, wherein the pHvalue of the composition is below
 4. 8. Composition according to claim4, wherein the acid(s) is (are) selected from the group consisting ofphosphoric acid, amidosulphonic acid and mixtures thereof. 9.Composition according to claim 4, wherein the surfactant(s) is (are)selected from the group consisting of quaternary ammonium salts, amines,amine oxides, betaines, sulpho-betaines and mixtures thereof. 10.Composition according to claim 1, wherein the composition contains atleast one builder or a builder system, at least one alkaline oralkalizing compound or mixtures thereof.
 11. Composition according toclaim 10, wherein the builder(s) or the builder system or the alkalineor alkalizing compound(s) is (are) present in a concentration of from0.5 to 6% by weight.
 12. Composition according to claim 10, wherein thesurfactant is at least partially a cationic surfactant.
 13. Compositionaccording to claim 1, wherein the compound promotes phase separation byseparating the salts.
 14. Composition according to claim 13, wherein thecompound is an alkali metal, earth alkali metal or ammonium salt of aninorganic acid.
 15. Composition according to claim 14, wherein thecompound is sodium chloride.
 16. Composition according to claim 1,wherein the compound contains an anionic surfactant, xylol or cumolsulphonic acid or salts or mixtures thereof.
 17. Composition accordingto claim 1, wherein it contains at least one perfume.
 18. Compositionaccording to claim 1, wherein it contains at least one coloring agent.19. A method for cleaning a hard surface which comprises applyingthereto a liquid detergent or cleansing composition which separates intotwo aqueous phases when left to stand, containing at least onesurfactant in a concentration of less than 10% by weight, containing atleast one electrolyte in a concentration of less than 15% by weight, andcontaining at least one other compound which promotes phase separationand comprises at least one hydrophobic element and at least one anionicgroup, provided the composition contains, if any at all, less than 10%by weight of organic solvent and less than 6% by weight of sodiumhexametaphosphate.
 20. A method according to claim 19 in which thecomposition additionally comprises at least one acid for removinglimestone deposits.
 21. A method according to claim 20 in which the acidis amidosulphonic acid.
 22. A method for washing soiled fabric whichcomprises immersing said fabric in an aqueous washing medium whichcomprises a liquid detergent or cleansing composition which separatesinto two aqueous phases when left to stand, containing at least onesurfactant in a concentration of less than 10% by weight, containing atleast one electrolyte in a concentration of less than 15% by weight, andcontaining at least one other compound which promotes phase separationand comprises at least one hydrophobic element and at least one anionicgroup, provided the composition contains, if any at all, less than 10%by weight of organic solvent and less than 6% by weight of sodiumhexametaphosphate.
 23. A method according to claim 22 in which thecomposition additionally comprises at least one acid for removinglimestone deposits.
 24. A method according to claim 23 in which the acidis amidosulphonic acid.
 25. A liquid cleansing and detergent compositioncontaining at least one surfactant, an electrolyte which promotes theseparation of said composition into at least two aqueous phases, andcontaining at least one other compound which promotes phase separationand comprises at least one hydrophobic element and at least one anionicgroup.
 26. A liquid cleansing and detergent composition which comprisesat least one surfactant, at least one limestone-removing acid and xyloland/or cumol sulphonic acid or salts thereof to promote separation ofsaid composition into at least two aqueous phases.